Reaction products of a polyhydric alcohol and a triazine derivative and methods of preparing the same



Patented Sept. 6, 1949 UNITED STATES PATENT OFFICE REACTION PRODUCTS OF A POLYHYDRIC ALCOHOL AND A TRIAZINE DERIVATIVE AND METHODS OF PREPARING THE SAME Frederic C. Schaeter, Stamford, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application December 20, 1948, Serial No. 717,606

1': Claims. 1

where It represents a number of the class consistlng or hydrogen and monovalent hydrocarbon radicals and R represents a monovalent hydro- (carbon radical (e. g., z-amino-lfi-dimethoxy- 1,3,5-triazine, 2-amino-4,6-dialloxy-1,3,5-trlazine, 2-cyclohexylamino-4,6-dimethoxy 1,3,5-triazine, etc.) and (2) a polyhydric alcohol in which the hydroxy groups are members the class consisting of primary and secondary hydroxy groups (e. 8., glycerol, ethylene glycol, dlethylene glycol, propylene glycol, dipropylene glycol, etc.) the hydroxy groups being the only reactive functional groups which are present in the said polyhydric alcohol. In certain cases it is desirable to use triazine derivatives wherein R represents hydrogen, that is. compounds represented by the general formula 2 where R represents a monovalent hydrocarbon radical.

Illustrative examples of monovalent hydrocarbon radicals which R (Formula I) and R (For- 5 mules I and II) may represent are: aliphatic (e. g., methyl, ethyl, propyl, lsopropyl, butyl, isobutyl, sec.-butyl, butenyl, amyl, lsoamyl, hexyl, octyl, decyl, dodecyl, octadecyl, allyl, methallyl, crotyl, oleyl. linalyl, etc.), including cycloalil0 phatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g., phenyl, biphenylyl or xenyl, naphthyl, etc.) aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, z-butenylphenyl, tert.-butylphenyl, etc.)

16 and aryl-substituted aliphatic (e. g., benzyl,

cinnamyl, phenylethyl, tolylethyl, phenylpropyl, etc.).

It is an object of the present invention to prepare a new class of synthetic materials, more par- 20 ticularly resinous compositions, which have par- 26 cially suitable for use in such fields.

Another object of the present invention is to prepare a new class of linear polymeric materials of the thermoplastic type, but which can be rendered thermosetting or potentially thermosetting 30 by reaction with an aldehyde, specifically formaldehyde.

A further object of the invention is to provide an economical and eflicient method by which the new synthetic materials described in the first paragraph of this specification may be prepared.

Other objects of the invention will be apparent to those skilled in the art as the description of the invention proceeds.

It was known prior to my invention that a '40 triazlnyl ester diflerent from those embraced by Formula I, specifically trimethyl cyanurate. could be transesteriiled with a monohydric alcohol. Thus, Hotmann [Ber. 19, 2061-2083 (1886)] observed that it trimethyl cyanurate is refluxed with an equivalent amount or sodium ethoxide in ethanol, it is completely transformed to the triethyl ester. However, to the best of my knowledge and belief, the reaction, more particularly a transesteriilcation reaction, between a polyhydric alcohol and a triaaine derivative of the kind embraced by Formula I to yield resinous materials, specifically linear polymeric resinous materials, varying in properties from liquids to hard, brittle resins was not known prior to my invention.

In practicing my invention reaction is effected between ingredients including a triazine derivative of the kind embraced by Formula I and a poLvhydric alcohol, preferably a dihydric alcohol, in which the hydroxy groups are either all primary or all secondary or some primary and some secondary. The reaction is essentially a transesterification reaction. especially ii conducted under heat at a temperature not exceeding about 155 C. In a transesteriiication reaction between a triazine derivative such as is covered by Formula I and a polyhydrlc alcohol several side reactions can occur, especially at temperatures at and above about .165 C. These are: (1) molecular rearransement oi the triazine derivative to an inactive form; (2) autoalkylation of the trlazine derivative with resultant iormation of hydroxy- 1,3,5-triazines which destroy or tend to destroy any alkali metal or alkali-metal alcoholate used as a catalyst for the reaction; and (3) replacement of the amino group attached to the triazlne nucleus by the polyhydric alcohol, thus giving rise to three-dimensional polymers. None of these side reactions requires a catalyst. However, all of these reactions are slow with most of the triazine derivatives embraced by Formula I and all can be efiectively avoided by carrying out the transesteriilcation reaction at a temperature not exceeding about 155" C., and preferably below 150 C. during all or most of the reaction period. In practicing my invention to obtain linear polymeric materials, I therefore prefer to conduct the reaction between the triazine derivatives and the polyhydric alcohol tairly rapidly at a relatively low temperature, thereby either obviating such side reactions substantially completely or reducing them to a minimum.

As indicated above, a reaction between the triazine derivative and the polyhydrlc alcohol will proceed under heat in the absence of a catalyst. However, in the preparation oi linear, polymeric, resinous materials a catalyst for the reaction ordinarily is employed, the kind and amountoicatalystbeinssochosenthatthereaction will proceed in the desired direction with a minimum formation or undesired by-products. As catalysts for the transesteriflcation reaction, I prefer to use a member of the class conslstlna of alkali metals, more particularly sodium, potassium, lithium, rubidium or caesium (or mixtures thereof), and alcoholates oi. alkali metals (or mixtures thereof) The catalyst may be employed in the form oi a mixture of an alkali metal and an alcoholate or such a metal. I! the catalyst is not initially in the form oi an alkalimetal alkoxide or alcoholate, the latter is formed when the alkali metal is dissolved in the polyhydric alcohol reactant.

The amount of catalyst may be varied over a wide range depending, for example, upon the particular triazine derivative and polyhydric alcohol employed and the particular pr p rties desired in the finished product. Ordinarily, however, the catalyst is used in an amount, calculated as alkali metal. e. g., sodium, corresponding to at least about 1.5 mol per cent, preferably from 2 to 10 or 12 mol per cent, or the molar amount 01 the triasine derivative employed. The use or higher percentages of catalyst is not precluded, but no particular advantage accrues therefrom. Optimum results have been obtained when the amount or catalyst, calculated as alkali metal, was from about 4 to 8 mol per cent of the molar amount of the triazine derivative used. The amount of catalyst required to give optimum reaction conditions with different triazine derivatives appears to increase in the order 01' increasing acidity oi the amino group attached to the triazlne nucleus.

The proportions or the triazine derivative and the polyhydric alcohol may be considerably varied, e. 3., from approximately equimolecular proportions 01' each reactant to from 2 or 3 mols or the polyhydric alcohol, a. g., a glycol, per mol oi' the triazine derivative. I prefer to use the polyhydric alcohol and triazine derivative in approximately stoichiometrical proportions. Thus, when the polyhydric alcohol is a dihydric alcohol, the reactants preierably are employed in approximately equal molar proportions.

The reaction may be eflected in the presence or absence of an inert solvent, that is, a solvent which is inert during the reaction, e. g., benzene, toluene, xylene, dioxane, anisole, etc. Ii an inert solvent or a substantial molecular excess of polyhydric alcohol is employed, the reaction may be carried out at atmospheric pressure. If an inert solvent or a substantial molecular excess of polyhydric alcohol is not employed, then the reaction advantaseously is conducted in large part under reduced pressure, e. g., from 750 mm. down to 0.5 mm. pressure, the lower pressures being employed at least toward the end of the reaction period. The pressure may be adjusted as desired or as conditions may require in order to eflfect the reaction without substantial decomposition of the reactants and to remove, e. g., by distillation, the volatile matter, more particularly the by-product alcohol, from the reaction vessel as transesteriflcation between the reactants proceeds.

The general reaction involved in the preparation oi linear polymers from triasine derivatives or the kind embraced by Formula I and polyhydric alcohols may be illustrated by the following equation in which a dihydric alcohol is shown as the alcohol employed:

In the above equation it and B have the same meanings as given above with reference to Formula I and R" represents the hydrocarbon chain of a dihydric alcohol. Surprisingly, such a reaction does not occur when R in the formula for the starting triazine derivative represents hydrogen.

In most cases the reaction starts at about 70 or 80 C. and usually about 50% of the by-product alcohol, which is indicative of the extent of the reaction, is removed at a temperature around 100 to 130 0. Generally, the reaction is slower and less complete when high temperatures (e. g., around 180 C.) are used from the start. If a reaction product which is essentially linear in structure be desired, it may be obtained by heating the reaction mass, preferably under reduced pressure, at a final temperature of approximately 140 to 155 0., preferably at about 140 to 150 (3., until no more alcohol is evolved. The total time or reaction will vary considerably dependins. for example, upon the size of the batch, the particular reactants employed and other influencing factors. Ordinarily, however, the transesterification reaction to obtain linear polymers is completed by heating the mixed reactants in the presence of the catalyst under reduced pressure at from about 70 to 155 C. ior about V to about 5 or 6 hours.

The linear polymers produced by my invention vary from liquid compositions to resinous materials which are solid or semi-solid at room temperature. In general, the products are softer as glycols oi higher molecular weight are used. Decamethylene glycol appears to react more sluggishly than triethylene glycol or diethylene glycol. This is in accord with the somewhat greater reactivity of the hydroxyl groups in the polyethylene glycols as shown in other reactions, as

for example the reactivity toward sodium. Surprisingly 2-ethyl-l,3-hexanediol reacts more rapidly than other glycols tested, despite the fact that one hydroxyl group is secondary. The melting point also may be lowered by employing triazine derivatives wherein the amino group attached to the triazine nucleus is substituted with a monovalent hydrocarbon radical. Greater substitution of the amino group also increases the solubility of the resin in organic solvents, e. g., solvent naphthas, benzene, toluene, xylene. butanol. amyl acetate, methyl ethyl ketone, ethylene glycol monoethyl ether, ethylene glycol. etc.

If a more complex resinuous material, that is, one containing a lesser amount (if any) of linear polymers, be desired, it may be obtained by heating the reaction mass substantially above 155 (3., e. g., from about 165 to 200' or 210" C. or more, for a prolonged period under reduced pressure or at a lower temperature at atmospheric pressure. This high temperature reaction may be effected in the presence or absence of solvents as described above with reference to the production of linear polymers. The reaction as temperatures above about 165 C. produces or tends to produce three-dimensional polymers, that is, resinous materials which are thermosetting or potentially thermosetting. It is possible that this is due to a reaction between the amino group of the triazine nucleus and the polyhydric alcohol at the higher temperatures.

In some cases it may be desirable to use a mixture of triazine derivatives of the kind embraced by Formula I instead of a single triazine derivative. In this way, and as is shown by some of the examples which follow, the reactivity of a slug- EXAMPLE 1 AWOL Parts 01 Ratio 2-Amino-4,$dlalloxy-i,3,5-triazlne 416 2 Triethylene gl col Sodium .Z f: -3

In a reaction vessel provided with a stirrer. a thermometer and a fractionating column were placed the above-stated amounts of triethylene glycol and metallic sodium. The glycol was warmed slightly until the sodium had dissolved, that is, had reacted with the glycol to yield a sodium alcoholate in solution in the unreacted glycol. The above-stated amount of Z-amino- 4,6-dialloxy-1,3.5-triazine was then added. The stirrer was started and the reaction vessel was heated under reduced pressure (about 50 mm.) at about to C. After heating for three hours, the theoretical quantity of allyl alcohol was obtained. The resulting transesteriflcation prodnot was a polymeric. brown, brittle solid, which softened at IMP-120 C. It was soluble in n-butanol, ethylene glycol monoethyl ether and cyclohexanol, but was only very slightly soluble in benzene, acetone, carbon tetrachloride and heptane.

A method of preparing 2-amino-4,6-dialloxy- 1,3,5-triazine and other unsaturated monohydric alcohol esters of ammelide is given in the copending application of James R. Dudley, Serial No. 700,840, flied October 2, 1946.

To 106 parts of diethylene glycol were added 156 parts of 2-amino-4,6-dimethoxy-1,3,5-triazine and about 32 parts of methanol containing 1.84 parts of metallic .sodium. The mixture was stirred and heated under vacuum as follows:

Total Time, 111 Hours BEES-7583 o,4e1,1ee

8 weight of about 302. The reectlm conditions were as iollowe Temp. mm 0. m

mm 'lheyieldoithereeinomizanleltu'iiicaflm product,whichwaeeoi'terthantheproductot EXAMPLE 8 u mamplegwu mtparte.

Mm. Pressure The Total Time The treneeetcrificetion product of this example was softer than the produetoi' Example 5. yield amounted to 1050 parts.

01 Ill 1mm The yield of me 0 am. a

m mm eem New" mm wm Mm m mm mummuum mm mm.

WWW... omoummm WNW m mm m period 1 total of about so: i or 1 4 0opartemethenoi). -..--l

During the reaction 89 parts of distillate was obtained.

lene GI I!!! m.

hmreuwsae'maeuzz'mcm The same procedure was followed as described 50 under Example 2. The reaction conditions were as follows:

the resinous transesteriilcation product was 251 35 fl-xerfino-l. 6-dimethoxy-1,3,5-triezine.-- II o I Bod! fl-Amlno-Ml-dimethoq-l, Oarbowax Compound 1 Sodium (in 32 parts mlyethylene (lyooll. had an avenue molecule:

Total Time u ELm'IJFhggQmmMQWMhMWWMIMdM The same procedure was followed as described under Example 2. The reaction conditions were '0 ea iollows:

Durin: the reaction period a total 0! about 102 parts of distillate was obtained. The tromesterincation product was dark in color and had "a wax-like appearance at room temperature. he

Mm. Preem weight oi about 1.

M 12 ll ocular 75 yield amounted to 1525 pertl.

'lotal'lime The resulting resinous traneesieriflcetion product was nearly clear and slightly soft at room temperature. It was soluble in water. A yield of EXAMPLE 5 some as Example 4 with the exception that 906.3 parts oi Polyethylene Glycol 300" was used "Polyethylene Glycol 200." The Poly- 1' which is predominantly 970 parts of this resinous composition was obhexeethylene glycol. hed an average moi .in place of ethylene Glycol 300 EXAMPLE 8 Parts Ratio fl-Amlno-l, 6-dimcthoxy-l,3,5-triazins use 0 l Hexamethyleue glycol I18. 0 1 Sodium (in about 17.6 parts methanol) 1. 0i

The same procedure was followed as described under Example 2. The reaction conditions were as follows:

Total Time Remarks Heat on. Glycol melted; vacuum 37 min 100 115 Temp. raised and pres sure lower-e 55 min 150 62 Solid mass in reaction vessel. Temp. raised.

1 hr. and 8 min 194 62 Resin melted.

2 hrs. and 8 min- 195 3 Heat oil.

The reaction product, when cool, was a hard, cloudy resin. The yield amounted to 225 parts.

EXAMPLE 9 rox.

Parts 0] Ratio 2-Amino-4, 6-diethoxy-l,3,5-triazine 184.0 1 Dietbyleno glycol 106.0 1 Sodium 2.0

The sodium was dissolved in the diethylene glycol, after which the triazine derivative was added thereto. The mixture was heated while under the vacuum produced by a mechanical pump as follows:

Total Time, in Minutes Same as Example 9 with the exception that -ethanol was obtained as a distillate.

l0 4 parts metallic sodium was used. The time and temperatures of reaction were as follows:

Total Time, In Minutes During the reaction period a total of about 77.5 parts of distillate (ethanol) was obtained. When cooled to room temperature, the reaction product was a hard, brittle resin. This resin was heated in a receptacle placed in an oil bath maintained at about 200 0., and dy nitrogen was bubbled through the resin, which was just soft at about 200 C., for about 18 hours. The resin did not become discolored following this treatment. The treated resin also was hard and brittle when cool. It was soluble in formalin.

EXAMPLE 1 1 A rox. Parts ol Ratio 2-Amino-i,6-diethoiry-l,3,&triazine 662 l Hexamethylene glycol 354 1 Sodium (in about 8 parts ethanol) 3 Essentially the same procedure was followed as described under Example 2. The reaction conditions were as follows:

Totai Time Remarks Started heating; Clear melt. acuum on and ethanol began to distill.

Temp. raised and pressure reduced.

15] Heat 01!.

The amount of distillate obtained during the reaction period was about 270 parts. The transesterification product, when cool, was a hard, brittle, opaque resin.

EXALJPLE 12 Parts i -Amino, 6-diethory-l,3,5-triszlue. 184 i Dwamethyiene glycol 174 1 Sodium (in about 18 parts ethanol) l A mixture of the above ingredients was heated for 1 hour at -125 C. under a pressure of 75-100 mm., during which time about 60 parts of After standing for about 16 hours at room temperature, heating was continued for two more hours at about C. under a pressure of 2-5 mm., during which time an additional 22.5 parts, making a total 01 11 about 82.5 parts. or ethanol was obtained. The resulting resin, which was obtained in a yield amounting to 288 parts, was light yellow in color and sticky at room temperature.

EXAMPLE 13 A Parts 01 Ratio Total Time Remarks Beat on. Vacuum on.

Full vacuum. .5 parts distillate obtained.

52.5 puts distillate obtained. 05 parts distillate obtained.

The last parts of the distillate was almost all unreacted z-ethyl-lx-hexanediol. When cool. the resinous product, was hard but sticky. It was obtained in a yield amounting to 250 parts.

The metallic sodium was added to the ethylene glycol, and after it had dissolved the triazine derivative was added. The mixture was heated as described under Example 13. At 100' 0. there was a vigorous evolution of methanol. After heating under vacuum for 1 hour at 100 C., 70% of the theoretical amount of methanol had been evolved. The transesteriflcation product was a hard. brittle resin.

The 2-cyclohexylamino-4.6-dimethoxy13,5- triazine was prepared by pouring a hot solution of 105 parts of cyanuric chloride in about 310 parts or acetone into 1000 parts of cracked ice. The temperature oi the resulting slurry was 10 C. To it was added 99 parts of cyclohexylamirle in 10 minutes with the temperature rising to 5 C. and the mass becoming neutral very quickly, after which 53 parts oi sodium carbonate was added thereto. The temperature slowly increased to +10 C. where it was held by means of an ice bath. and carbon dioxide was evolved over a 2-hour period. The product, 2-cyclohexylamino- 4,6-dichloro-1,3,5-triazine, was an oil that was separated, washed with water and dried in a vacuum desiccator.

A solution of 50 parts of sodium hydroxide in about 500 parts of methanol was prepared, and to 12 itwasslowlyaddedi'npartsoltheaboveoil while cooling the mass to keep the temperature at 3540 C. Themixturewasthenrefluxedior sominutesandiilteredhot. Onoooling.irnpure crystals of fl-cyclohexylarnino-dn-dimethoxyl,3,5-triazine separated from the filtrate. The yleldwasincreasedbydilutingtheilltratewith water. The solid was recrystallised tram hot 50% methanol and dried at C. The purified 2 cyclohexylamino-4,0--1.3Ji-triaxine had a melting point or 12'l-120 O. A small sample recrystallized lrom hot 50% acetone gave a melting point of 129 C.

. P- M iii Ratio S-Octsdecylamino-i,&dimethoxyl,3,5trlaline---.. us 1 Polyethylene Glycol 300" m 1 Sodium 1.s

The sodium was added to the polyethylene glycol, and the resulting mixture was heated at about 100 to C. until the sodium had dissolved. The triazine derivative was now added, and the reaction mass was heated with stirring under reduced pressure for about 12 hours at a temperature ranslns from about 00 to 155 C. and a. reduced pressure of the order of about 10 to about 17 mm. For about 7 hours oi. this reaction period the reaction mass was at a temperature of about to C. About 32.3 parts of distillate was collected during this reaction period. The yield of the 1 tion product amounted to 514 parts. It was a soft, brown resin, and gave a cloudy dispersion in water.

2-octadecylamino-4,0-dimethon-1,3,5-triaaine is prepared, tor example, by adding 108 parts of sodium bicarbonate and 105 parts of cyanurio chloride to 500 parts of a solution containing 00% methyl alcohol and 10% water. The mixed ingredients are allowed to react at 30 to 35 C. until the evolution or carbon dioxide has diminished. after which the reaction mass is heated to reflux temperature in 15 minutes and thereaiter refluxed for 25 minutes. The resulting Z-chloro- 4,6-dimethoxy-1,3,5-triaaine is cooled to 85 0.. after which 260 parts 01' octadeeylamine is added slowly while cooling the mass, followed by the addition of 84 parts of sodium bicarbonate. The resulting mixture is heated under reflux at the boiling temperature or the mass for 1 hour. cooled, diluted with water and filtered. The crude, waxy 2 octadecylamino-4,0-dimethoxy-1,3,5-triasine produced in this manner is mixed with 1000 parts or a 1% solution of sodium hydroxide, warmed to 70 C. and then allowed to cool slowly. The solid layer that separates is removed. washed with water and dried at 50 0., thereby yielding purified 2-octadecylamino-4,6-dimethoxy-1,il,5-triasine.

The sodium was added to the polyethylene glycol, and the resulting mixture was heated at 100 to 125 C. until the sodium had dissolved. The triazine derivative was now added, and the mixture heated with stirring under vacuum ior about 11 hours at a temperature ranging from about 70 to 150 C. and a reduced pressure varying from about 70 mm. down to 12 mm. For about hours of this reaction period the reaction mass was at a temperature 0! approximately 145 to 150 C. and at a pressure oi the order 01 12 to 13 mm. The yield 0! distillate amounted to about 36.2 parts. The transesteriflcation product, which was a soft, cloudy, brown, resin, was obtained in a yield amounting to 495 parts. It was dispersible in water.

The 2-dodecylamino-4,6-dimethoxy-1.3,5-triazine is prepared in essentially the same manner as described under Example 15 with reference to the production of 2-octadecylamino-4,6-dimethoxy-1,3,5-triazine. However, in this case the crude product was dissolved in ether and then washed with dilute alkali and water. The ether was evaporated by heating the washed material on a steam bath, and drying the purified product in a vacuum desiccator over sulfuric acid.

The sodium was dissolved in the ethylene glycol in a 3-necked reaction vessel provided with a stirrer and a i'ractionating column, after which the triazine derivative and benzene were added thereto. The mass was heated under atmospheric pressure. A constant boiling mixture boiling at 56 C. and which contained about 39% of methanol, by weight, was distilled off. After iurther heating under atmospheric pressure at a bath temperature of 120 C. for 2 days, approximately 50% of the theoretical amount of methanol was obtained, leaving the primary product of the heated for 4 hours and minutes within the temperature range 01' 155 to 192 C. (most of the time at 155 to 176 C.), during which period an additional 20% 01' methanol was collected. The odor of ammonia given 01! toward the end of the reaction period indicated that side reactions were taking place in addition to the primary reaction between the glycol and the triazine derivative. A solid reaction product which was partially The same general procedure was followed as described under Example 18. After heating the reaction mixture at atmospheric pressure for 75 minutes at 100 to 135 0., approximately 59.2% of the theoretical amount 01' ethanol was collected. Additional heating and further amounts oi! sodium did not increase the amount of ethanol evolved.

EXAMPLE 20 Awe; Parts 01 Rario 2-Butylamlno-4,0-dimethoxy-i,3,5-tria1.ine 700 l Ethylene glycol 410 2 Sodium 5 The reaction of a mixture of the above ingredients went 50% to completion upon heating at atmospheric pressure for only 20 minutes at 107 to 124 C., after 15 minutes heating to bring the mass to reaction temperature. Heating for an additional 3 hours and 40 minutes at 124"- 154" 0., including about 3 hours and 25 minutes at 150-154 (2., produced a total of 82.5% of the theoretical amount of methanol. The excess, unreacted glycol is removed by heating the mass under reduced pressure. The reaction product of this example was soluble in alkali, indicating reaction. This example illustrates the prepara- .50 t t a substantial quantity of hydmxytflazmes tion of a reaction product by reacting the triawas present t m zine derivative and the polyhydric alcohol, spem 21 ciflcally ethylene glycol, in the presence of an inert solvent.

EXAMPIE 1e Parts it? Ratio A inn-4,0-di thory-l,3,5-trl in 520 1 Parts 25 laie t hylene gly asl it: 710 2 Ratio Bum-ml 5 2-Amino-4.6-dimethoxy-l,3,Mriazine no 1 The sodium was dissolved in the glycol and 533%???311::::::::::::::11:11:: .13: 2 2 the meme derivative added heating the resulting thick paste at atmospheric pressure for 10 minutes at to 0., approximately 41% of the theoretical amount of methanol was distilled from the reaction mass. Further heating for about 3% to 4 hours at a maximum temperature of C. caused the reaction to proceed to 65.4% completion as indicated by the amount of methanol collected. A solid material that was somewhat softer than the product of Example 10 was obtained.

EXAIJPLE 22 Same as Example 21 with the exception that 18 after bringing the reaction mixture to a temperature of 115 C. in 15 minutes. further heatingwascontlnuedunderareducedpressureoi 210 mm. down to 100 mm. at a temperature of 115 to 150' C. for a total of 128 minutes. During this heating period 80% oi the theoretical amount or methanol was evolved. A clear. almost colorless reaction product was obtained.

exams: 23

a m ol am ws-o-hnm m 1 "Poiyeth l 1.3: 1 Sodium wmmm liltpertsmethanol)... 1o

The above ingredients were mixed and heated together at atmospheric; pressure for a little over 6 hours at a temperature or 124' to 130 C.

In the following Examples 20 to 31, inclusive. the glycol was introduced into the reaction vessel and the indicated amount 01' metallic sodium was dissolvedintheglycohbyheatlngiinecmsary. (In some cases; the sodium was introduced as sodium methoxide in a measured volume 01' methanol.) The aminodialkoxytriasine was then added. and the vessel was fitted with a stirrer and distilling head. A condenser, a receiver cooled in Dry Ice, and a pumping system were arranged in the usual manner for low-pressure distillation. The reaction vessel was heated by an oil bath, and the pressure in the m was ad- Justed by means 01 a variable leak in the pump line. The pressures used depended upon the rate of evolution of methanol, the boiling point oi the glycol. and the foaming tendencies of the reaction mixture. Usually of 200-400 mm. were used at the start of the reaction, and

20 the pressure was decreased gradually to 1-10 mm.

Approximately 48.5% 01' the theoretical amount of methanol was collected during the formation of the resinous transesteriilcation product.

Aite'r heating the mixture of the above ingradients for 8 hours at 113' to i" C. under a reduced pressure of about 200 mm. and i'or about 1 hour at 150 0. under a reduced pressure oi about 10 mm., approximately 152 parts of ethanol was collected. An additional 16 parts or ethanol was obtained when the reaction mass was heated for an additional 8 hours at 150' C. under a pressure oi about 12 mm. The total quantity oi. ethanol collected was 72% of the theoretical amount. The reaction product was a clear. yellow, tacky, reslnom material.

at the end.

The degree of reaction at any time was calculated from the weight oi material lost from the reaction vessel (or iound in the receiver). The

2 identity of the volatile material was checked by the refractive index of the distillate. In certain cases where glycol was carried out of the reaction vessel by the methanol evolved, the composition or the distillate was calculated from its refractive index, and the degree or reaction calculated from this composition.

By the term "efl'ective time mentioned in the tables is meant the number 01' hours of heating during which the resin-forming reaction took place. The degree or reaction is calculated on a basis or for complete displacement or the simple alcohol from the reaction mixture. However, the sodium retains an equivalent amount or simple alcohol and glycol as alkoxide. Therefore, for example, if 10 mol of sodium (based on the molar amount 01' triozine derivative) is used as the catalyst, the upper limit for the degree of reaction as given in Examples 25 to 31, inclusive, is approximately 97.5%.

EXAMPLE 25 Ream from z-ornino-sj-dibutocv-Ldj-triazine llol Per Ont W Reaction Oonditims Glycol (Based m (Hm .0 mm) Description at ltesimus Product Ultfl) 1.5 hrs. at 12) at 14mm.--" 48 new... r:.: -::s:::-: :2 mere-:1"re arches ma min..--. sou n e yenegyoo monom $1.5 hrs. at 170' at 1 2mm... 80 soluble in butanol, M. P. es. ill 0. y

l in. at 170' st1-2mm.. 88

0. 6 hrs. elective time.

21m. at mm 56 v ery herd, brittle, soluble in etll lane glycol monom I: :2: {1: 2:11:1 3;, methyl t r. insoluble in m l hrs. eileetive time.

1 hr at18lstmmm--- ill Tan-colored in solid, soluble in eth l 'lriethylene glycol.... 10 h a: 1& 5::: '1 5 monometliyl et h sr, insoluble in butanoL 8. I hrs. elective time.

0.5 hr. It 117' It 1M mm.--- 82 ms-t::; a:

Moderately soft solid, very dark color soluble in Do 4 2 1:: 3'1: :2 ethylene glycol monomcthyl ether, insoluble in in 0 hr. at 1w at 1-2 at ll hr. at 178' at l-2 mm..--- 87 4. 75 hrs. elective time.

The 2-amino-4,8-dibutoxy-1,B,5-triazine is prepared. for example. by heating for 2 hours at 80' C. a mixture or 1 mol of wet 2-amino-4,6-dichloro-1,3.5-triazine. 800 cc. butanol and 2 mols NaOH. The product is isolated by crystallization from the hot filtrate and evaporation of the illtrate. It has a melting point oi 100 C.

sible. The crude 2-diethylamino-4,6-dichloro- 1.3,5-triazine is dried in a vacuum desiccator over sulfuric acid. It has a melting point of 76-78 C. A small portion 01' this product, after recrystallization lrom a syrup in benzene yields large needles which melt at '17.5-"i9 C.

One hundred and forty-three (143) parts of the dry, crude 2-diethylamino-4,6-dich1oro-1,3,5- triazine is dissolved in about 238 parts of acetone,

Resin from Z-omino-LG-dImcthOru-IJJ-triaaine l and this solution is added over a period of 30 in 1. .l

W (1 l I on my; 933mg, Reaction Description of Besinous Product TB! 6 Per Cent Used) 31;: E ii N alien ard r. a a nun. o as H brittle s1 tiy cloud 1! hi oolor eolubl in mm 1ml 4 $1. 0 hr. at 140 at 2mm to ethylene ziy moneme 'yl other, insoluble in 1 0 hr. at155 at 2 mm 75 butauol. (+1 0 hr. at 180 at 2mm) No change 3.5 hrs. eflective time.

Reactante were completely compatible only alter 2.5 hrs.

EXALIPLE 27 Resins from 2-diethulamino-4.6-dimethozu-1,3,5-

triazine Mgl l eroent D I um agree 0 Reaction Conditions (Hours at G] l Based on Reaction Descrl ti oi nous P r I1 um o. at mm.) Per cam m Used) 0. 33 t 7 Tflgthylem glymL 4 0 n 2: iia f; g F1651, brown syrup; V01! V1800.

0. 83 hr. eiiective time.

set-st rner a 3 64 0 us we: Reaction mixture became u e its Ethylene zlyool 6 {1: 73 1} Wm fieawd 21m.) olmq a r 2. 25 hrs. eflective time. +2-2.r.=*:r; 2 he as i B 1 at m 92 l Dietliylene g yooi +0 25 hr. at 160 at 2 mm h H I cum. so uble in butane] 1.5 hrs. efleetive time.

Hziiohfie. attlflg at 25-2 mm. 87 5 Dmethyhne glycol 10 +2 0 t 2K 2 32 ry viscous syrup, light color, soluble in butanol.

+2. Dine. at 180 at 1 mm. ap- 07.6 x.

6. 5 hrs. eflecti e timle.

attain-.et 120 at600mm 60 416% RtIg BttOgO-BDO mm- N 72 a 5 mm) Tan eolored, very viscous syrup soluble in butanol Decametbylene glyooi. 4 2: 3 a: 2: Egg g (The catalyst was insoluble at the end oi the reaction.)-

+2. 0 hrs. at 185 at 2 mm..... 93 +2.0hrs. at185 atfimm 90 8. 5 hrs. eflective time.

2-Ethyl-l,3-hexanediol.- 4 o 5 hr. at 120 at 4004mm 90-98 Very clear. iightoolomd, hard and brittle, melting point, ca. 66 0.

The 2-diethylamino-4,6-dimethoxy-1.3.5-triminutes to a solution of 41 parts of sodium hyazine is prepared, for example, by dissolving 553 parts cyanuric chloride in about 950 parts of hot acetone, and filtering the resulting solution into 1800 parts of well stirred ice water. To the resulting suspension of cyanuric chloride, 219.3 parts of diethylamine is added gradually over a period of 1% hours while the temperature of the reaction mixture is kept at 5 to 10 C. by external cooling. Sodium carbonate 159 parts) is then added at 5-10 C. over a period of minutes and thereafter the mixture is stirred for an additional 40 minutes at 0 to 5 C. The creamy mixture is then filtered, and the separated solid is droxide in about 478 parts methanol. During the time of addition, the reaction temperature is kept at to C. and following the addition the mixture is heated to C. for 2 V hours. The mixture is filtered hot, and the filtrate is evaporated to 250 parts which is then poured into 2000 parts of ice water. The oil which precipitates crystallizes after standing for 3 or 4 hours at room temperature. The crystals 0! 2-diethyiamino-4.6-dimethoxy-1,3,5-triazine are filtered, washed with water and dried over sulfuric acid in a vacuum desiccator. The crude product melts at 34-35 C. A sample recrystallized from benwashed with water and filtered as dry as posl5 zene melts at 3344 C.

EXAMPLE 28 containing additional triazine derivative is mixed Resin, from zhgnylamfno-4,fl-dimethory 1 3,5- with 4000 parts of water to dissolve the sodium mug chloride. The Z-phenylamino 4,0 dimethoxy- Moi rcent Bo i um Reaction Conditions (Hours Degree Glycol (Based on at O. at mm.) Reaction Description of Resinous Product Triazine Per Cent used) 1.5 hrs. at 120 at 200-2 mm. 09 l 1" 10 +1 hm at 200 M 2 m Moderately hard brittle, cloudy soluble in butanol Decamcthylene s W hrs at at 2 mm')" No chm M. P., ca. 50 6.

3.0 hrs.eflective time. 1 0.5 hr. at 100 at 20 mm. 58 rzss zs 2; z-Ethyl-lfl-hexanedloh. r. a 11 mm V 1 +055 hr. at at 501mm 78 cry c ear, red color, vo hard and brittle soluble in +1.5 me. at 100 at mm). Slight debmml' a composi- 215 hrs. eiiactive time. tion.

0.5 hr. at 120 at 760 mm. iii 2'- 153 2 2.8 r. e 3 mm 00 Trlethilme I Y 3 (+1.0 hr. at 150 at mm.) No change Hard brittle, clear, dark amber color, M. P. 0a., 50 0 +1.5 hrs. at we" at 15 mm.; (+3.0 hrs. M180 at 15 mm. Decomposition, 3.5 hrs. efleotive time.

The 2-p e yl fi-dim oxyri- 1.3,5-triazine is separated by filtration and puriazine is prepared. for example, by filtering into 5 mm, 1500 parts of stirred ice water a solution of 276.6 EXAMPLE 29 parts (or 295 parts of 96% soluble crude material) oi! cyanuric chloride in 584 parts of hot acetone, Resin from z-butulamino-dfl-dimethozy-l,5,5- and to the resulting suspension 139.5 parts of triasine 0 530 35111 Degree of u 0 am Glycol (gm 333 2: s gaggle; Description 0! Reeinous Product Used) 0.5 hr. at 115 at700-1601nm 62.5 so", tacky loudy, (The catalyst was insol ble t teasers-sisters; a: Madam 1. 5 his. efleotivc time.

aniline is added dropwise while the reaction mixture is kept at 3 to 6 C. by external cooling. Then 79.5 parts of sodium carbonate is added gradually at the same temperature, after which the reaction mixture is stirred for 1 hour at 0 to 5 C. The resulting crude 2-phenylamino- 4,6-dichloro-1,3,5-triazine is filtered as dry as possible, in which form it contains about 50% of water. This material, amounting to 725 parts, is added gradually at to C. to a solution of 123 parts of sodium hydroxide in about 950 parts or methanol. The mixture is then heated at C. for 2 hours. The hot reaction mass is filtered, and the filtrate is poured into 5000 parts 01' cold water. The oil which precipitates crystallizes at once, giving 180 parts of 2-phenylamino-4,6- dimethoxy-1,3,5-triazine, M. P. 128.5-130.5 6., after drying at 100 C. The insoluble residue The 2-butylamino-4,6-dimethoxy-1,3,5-triazine is prepared, for example, by filtering into 750 parts of ice water a solution of 93 parts of cyanurio chloride in about 198 parts of hot acetone. To the resulting suspension of cyanuric chloride 36.6 parts of butylamine (n-butylamine) is added dropwise while the reaction mixture is kept at 0 to 5 C. by external cooling. Then 26.5 parts of sodium carbonate is added gradually at the same temperature. The mixture is stirred for 1 hour after the reactants have been added. The resulting crude 2-butylamino-4.6-dichloro-1,3,5- triazine is filtered as dry as possible, after which it is dried in a vacuum desiccator over sulfilric acid to obtain a crude material having a. melting point of 4840" C. After recrystallization from benzene the melting point 01' the purified material is 5152 C.

22 mixture is maintained at 35 to 45' C.. external cooling also being employed. when the addition is complete, the mixture is heated slowly to 60 C. and kept at this temperature for 1% hours.

5 The hot mixture is then filtered and the filtrate is poured into 2500 arts of water. The precipitated oil crystallizes slowly at room temperature. The crude, crystalline Z-(N-methyl-N-phenylamino) -4,6-dimethoxy-1,3,5-triazine amounts to 10 115 parts after drying in a vacuum desiccator over sulfuric acid and melts at 46 to 47 C. A

30 purer product melting at 51-52 C. is obtained Resin from 2- (N-methul-N-phenulamino) -4,6- by redissoiving the crude material in hot methadimethoxu-Lij-triazine no], filtering the resulting solution, and repre- Mol Per sgi i R e11 Glycol fi g g? Emotion Desu'iption oi Resirioul Product mine Used) Wm M 4 train n s-11; s i m 1.5 hrs. eflectlve time.

The 2- (N-methyl-N-phenylamino) -4,6-dimethoxy-1,3,5-triazine is prepared, for example, by dissolving 553 parts of cyanuric chloride in about cipitating the compound by pouring the solution into water.

EXALEPLE 1550 parts 0! hot dioxane, and filtering the re- 31 suiting solution into 1800 parts of well-stirred ice Mixed resins 5%?! tB gl B ti 0 dlti D I Reecti Descri um sac on on one agree 0 on ti o! mime ont'iarlairiine (Hours at "0 at mm.) Per Cent keainourP r dnct 0.5 mol 2-(N-methyliznoltrieth l- 4 (st start). 0.5 hr. at 110 at 760-200 mun-.. 30 N-phenylamino)-4,B- one glyco +0.5 hr. at 125-130 at 60 mmi8 dimethoxy-l,3.5-triamixture became homozinc and 0.5 mol 2- geneous at this point. amino-4 0- diineth- +0.75 hr. at 140-150" at 10 mm 55 oxy-l,3,6-triasine. +2.0 hrs. at 5 at 10 mm 50 (+1.5 hrs. at 105 at 10 mm) iairiy clear. some Increased to +1.5 hrs. at 125 at 10 mm 66 amlnodimetboxy 8%. hrs. at ISO-100 at 10 mm... a sublimod. 0.5 mol taminoibdt lmoltrieth l- 8. 1.25 hrs. at 120 at 760-10 mm.... 877 ethanol reoovered Very light ol vary ethoxy-i,3,ii-triarine ene giyco 44 methanol recovered. clear, stiii syrup, and 0.5 mol 2-diethdoes not flow at room ylamino-LB-dimethtemperature. 0xy-1,3,5-triuzine. 08% ethanol recovered. +1.0 hr. at 140 at 10 mm 53 a Sign!!! recov- 1 ethanol recovered. +3.0 hrs. at 170 at 10 mm methanol recovered.

INN-79.5% reacted.

water. To the suspension of cyanuric chloride EXAMPLE 32 thereby obtained is gradually added 321 parts of methyianiline over a period of 1 hour while keeping the temperature of the reaction mixture at 4 to 8 C. One hundred and fiIty-nine parts of sodium carbonate is then added to the cold mixture to neutralize the hydrochloric acid formed by the reaction. The neutral mixture is filtered as dry as possible. The water that remains in the crude material is removed by heating it in a 100 C. oven. The dry 2-(N-methyl-N-phenylamino)-4,6-dichioro-1,3,5-triazine amounts to 702 parts and has a. melting point 01 1 -131.5 C. A sample recrystallized from benzene forms large, clear crystals, M. P. 130.5131.5 C.

One hundred and twenty-seven and one-half parts of the crude triazine derivative is added gradually to 41 parts of sodium hydroxide in about 475 parts 01 methanol. The rate of addi- The simultaneous transesteriflcation of two difierent compounds of the kind embraced by Formule. I, more particularly two diiierent aminodialkoxytriazines, with a polyhydric alcohol, specifically a glycol. is exemplified in this example wherein the results are shown below in tabular form. The resin-forming reactions were carried out as indicated hereinbefore. at optimum temthe mixed alcoholic distillate was calculated from its refractive index by using the known linear relation between the refractive index and the composition expressed in weight per cent of either component. In the table 2-amino-4,8-dition is such that the temperature of the reaction ethoxy-1,3,5-triazine and z-(N-methyl-N-phenylas ume 23 amino) -1,3,5-trialine are abbreviated to and MPADIIT, respectively. For purpose of blank preparations where a single triazine derivative was used are included in the 24 cation of Z-(N-methyl-N-phenylamino) 4,6 dimethoxy 1,3,5-triazine and 2 amino iii-diethoxy-i,3,5-triazine with triethylene glycol.

A mixture 01' 2- (N-methyl-N-phenylaminwtable. i ifi-dimethoxy-ififi-triasine and triethylene gly- Tnu I Simultaneous transesterification of two Z-aminolj-diolkomy-LSJ-tflozines with glycol:

o PerOentAioohol Evolvodaitor H Moi Per Gent Oom- (Na! at Optimum Temperature: m 1 oi 'irluine mols lmol Properties oi the Balloons Product 'irlasins i 2 s 4 mm AD 'I' 0.04

an 'r Z tits-e -fg -0 T ,33? 7 lisht colored and D MPADMT tsckysynip, clear md 11 mm g #2 ggg vg i 1:11 olear and um colored. D0

0.08 at? 7| M d "I!" sg ng'r'icu st m g i fim D0 p m'i -ifi: am Ind 18ml? MPADMT 8% My syrup, vary oleu' ma light- 2 Dieth iamino "T6" EtOH as loo I m -l,8,5-iri- M8 44 Moon I: a 3331:: m

0 snares 1.0 EtOlL. as Olear,

{armour 1'5 m 00H... 07. s

The foregoing results clearly indicate that in mixtures of certain triazine derivatives of the kind covered by Formula I, specifically 2-amino-4,6- diethoxy-Liij-triazine and 2-(N methyl N phenylamino) -4,6-dimethoxy-i,3,5 triazine, the reactivity of the former triazine derivative toward triethylene glycol is greatly enhanced by the presence of the latter which. however, reacts more sluggishiy than when it is used alone. In order to obtain a sufliciently high degree of reaction oi the latter triaaine derivative to produce a relatively high molecular weight resin, the molar ratio of 2-amino-4,6-diethoxy-i,3,5-triazine to 2 (N- methyl-N-phenyiamino) 4,6 dimethoxy 1,8,5- triazine should not be greater than about 1 to 3,

and the catalyst concentration should be approximately 4 mol per cent based on the total molar amount of triaxine derivative employed. Corresponding ratios and catalyst concentrations may be used with other mixtures of triazine derivatives of the kind embraced by Formula I, or the ratios and catalyst concentrations may be varied thereirom as desired or as conditions may require in order to obtain the desired reactivity of the mixed triaaine derivatives toward a particular glycol or other polyhydric alcohol.

It is to be noted that 2-diethylamino-4,6-dimethoxy-ifij-triazine also exerts a catalytic ettest on the reaction oi 2-amlno-4,6-diethoxy- 1,8,5-triazine toward a polyethylene glycol. Since triethylene glycol is a typical polyethylene glycol, the results are believed to be general for the simultaneous transesteriflcatlons oi polyethylene glycols with mixtures of two diflerent triazine derivatives of the kind covered by Formula I, in one of which the amino group is unsubstituted and in the other oi. which the hydrogen atoms of the amino nitrogen have been replaced by two of the same or diflerent monovalent hydrocarbon radicals to yield an N-disubstituted trlazine derivative.

EXAMPLE 33 This example shows the stepwise transesteriflcol (having dissolved therein 4 mol per cent of sodium based on the molar amount of triazine derivative) in the ratio of 3 mols oi the former to 4 mols oi the latter was heated under reduced pressure for '15 minutes at to C. The z-amino-4,6-diethoxy-1,3,5-triazine was then added together with an additional 4 mol per cent of a sodium based on the molar amountoi the triazine derivative. The resulting reaction mass was heated under reduced pressure ior 1 hour at (2., whereby 98% oi. the theoretical amount of methanol and 68% ot the theoretical amount of ethanol were obtained. After heating for an additional hour at C. and for 15 minutes at C. under reduced pressure, the yields of methanol and ethanol evolved were 100% and 89%, respectively. of the theoretical amounts. The resinous product was clear, light-colored, sort and tacky.

It will be understood, 0! course, by those skilled in the art that my invention is not limited to the specific polyhydrlc alcohols. triazine derivatives and catalysts named in the above illustrative examples. Thus, instead of sodium or an alcoholate or sodium as a catalyst, I may use any or the other alkali metals or alcoholates thereof. Other polyhydric alcohols in which the hydroxy groups are all primary or all secondary or some primary and some secondary may be employed, for example, glycerol, pentaerythritol, mannltol, sorbitol, dlpentaerythritol, 1,3-butylene glycol, pentaethylene glycol, heptaethylene glycol, octaethylene glycol, decaethylene glycol. polyvinyl alcohols, polyallyl alcohols. 2-butyl-L8-octanediol (2-butyl-3-pentyl-Lll-propanediol), 2-ethyi-2- methyloi-i-hexanol(2-ethyl-2-butyi-1,3-propanediol) 0-methyl-2,i-heptanediol( i-methyl-B-isobutyI-L3-propanediol) etc.

Illustrative examples of other triazine derivatives of the kind embraced by Formula I that may be used are:

2-methylamino-4,6-dialloxy-l,8,5-triaaine 2-allylamino-i,6-dimethoxy-l,3,5-triaxine 25 2-amino-4,B-diphenon-1,8,5-triazine z-amino-4,6-diphenylmethoxy-1,3.5-triazine 2-benxylamino-4,6-diethoxy-1,3,5-triazine 2-anilino-4,8-dipropoxy-l,3,5-triazine 2-amino-4,8-dipropoxy-1,3,5-triazine 2-amino-4,6-diisopropoxy-1,8,5-triazine 2-anilino-4,6-dimethoxy-l,3,5-triazine 2- (N-methyl-N-cyclohexylamino) 4,8 dimeth oxy-i,3.5-triazine z-(N-ethyl-N-cyclohexylamino) 4,6 dimethoiry- Buch compounds are prepared, for example, by methods such as described under some of the specific examples with reference to other compounds of the kind covered by Formula I. More detailed information on the preparation of some of these compounds also is given in the aforementioned copending application 01' James R. Dudley, Serial No. 700.840.

The resinous compositions of this invention may be modified in various ways, for example by effecting the reaction between the poiyhydric alcohol and the triazine derivative in the presence of various modifying agents. For instance, the reaction may be effected in the presence of a monohydric alcohol having a boiling point higher than the alcohol by-product of the reaction, or in the presence of waxes or wax-like bodies or various natural or synthetic resins or gums.

Certain of the linear polymers of the present invention, more particularly those which contain at least one hydrogen atom attached to the nitrogen atom of the amino grouping of the triazine .nucleus, are especially suitable for use in the preparation of thermosetting resinous compositions. For example, such polymers or polymers obtained by reacting a poiyhydric alcohol with a mixture of (1) a triazine derivative having an unsubstituted or partially substituted amino grouping attached to the triazine nucleus and (2) a triazine derivative having both of its hydrogen atoms of the amino grouping replaced by a monovalent hydrocarbon radical may be reacted with an aldehyde, e. g., formaldehyde, as more fully described and claimed in my copending application Serial No. 717,605, flied concurrently herewith.

The resinous materials or this invention also may be employed as modifiers, more particularly as plasticizers, of other synthetic resins, in order to impart toughness or improved plasticity to resins which otherwise are excessively brittle or have poor plasticity. They may be co-reacted with various aldehyde-reaction products, for example partial reaction products of an aldehyde, e. g., formaldehyde, and phenol or a substituted phenol, urea or a substituted urea, melamine or other aminotriazine, etc. They also may be incorporated into alkyd resins. For instance, the reaction between the poiyhydric alcohol and the triazine derivative may be eflected in the presence 01' an excess or the former, and the unreacted poiyhydric alcohol then may be esterifled with phthalic anhydride, maleic anhydride, fumaric acid or other polycarboxyiic acid or anhydride in the presence of the transesteriflcation product thereby to obtain a modified alkyd resin.

Other uses of the products of the present in vention include adhesive, casting, molding and coating compositions, as well as textile-treating compositions.

My new synthetic materials may be used alone or admixed with various fillers, pigments, dyes or other modifying agents, e. g., phenol-aldehyde resins, urea-aldehyde resins, melamine-aldehyde resins, alkyd resins, cellulose esters, cellulose others, hydrocarbon-substituted polysiloxane resins, etc. The soluble polymers may be dissolved in solvent naphtha, xylene, benzene, toluene, butanol, methyl ethyl ketone, amyl acetate, etc., to form coating and impregnating compositions or any desired viscosity. Such compositions may have incorporated therein linseed oil, tung 011, says. bean oil or acids thereof, or other drying or semi-drying oils or acids, as well as driers, more particularly metallic driers, e. g., cobalt naphthenate, manganese naphthenate, cobalt resinate, etc., to improve the adhesive and drying characteristics of the composition.

Chemical compounds represented by the general formula F N N 1 F R T where n represents an integer which is at least 1 and not more than 2, It represents a member of the class consisting of hydrogen and alkyl radicals containing at least 12 and not more than 18 carbon atoms, R represents an alkyl radical containing at least 12 and not more than 18 carbon atoms, and R" represents a radical which corresponds to the residue of a primary aliphatic monohydric alcohol are disclosed and claimed in the copendlng application of Dagfrid Holm-Hansen, Serial No. 717,593, filed concurrently herewith.

Chemical compounds represented by the same formula as Formula IV where n represents an integer which is at least i and not more than 2, R represents a member of the class consisting of hydrogen, lower alkyl radicals and cyclohexyl radicals, R represents a cyclohexyl radical and R" represents a radical which corresponds to the residue of a primary aliphatic monohydric alcohol are disclosed and claimed in the copending application of Pierrepont Adams Serial No. 717,- 589, filed concurrently herewith.

What I claim as new and desire to secure by Letters Patent of the United States is:

l. A composition comprising a synthetic material obtained by eflecting reaction under heat between ingredients including 1) a triazine represented by the general fromula where R represents a member or the class consisting of hydrogen and monovalent hydrocarbon radicals and R represents a monovalent hydrocarbon radical and (2) a polyhydric alcohol in which the hydroxy groups are members of the class consisting of primary and secondary hydroxy groups, the hydroxy groups being the only reactive functional groups which are present in the said polyhydric alcohol.

2. A composition as in claim 1 wherein R. represents hydrogen.

3. A composition as in claim 1 wherein R represents an alkyl radical.

4. A composition as in claim 1 wherein R represents hydrogen and R represents an alkyl radical.

5. A composition comprising the resinous product of a transesteriflcation reaction under heat between a 2-amino-4, 6-dialkoxy-1,3,5-triazine and a dihydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein.

6. A composition comprising a linear polymer obtained by effecting a transesteriflcation reaction under heat between 2-amino-4,6-dimethoxy- 1,3,5-triazine and a dihydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein.

7. A composition comprising a linear polymer obtained by effecting a transesterification reaction under heat between 2-amino-4,6-diethoxy- 1,3,5-triazine and a dihydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein.

8. A linear polymer which is the product or a transesterification reaction under heat between 2-amino-4,6-dimethoxy-l,3,5-triazine and diethylene glycol.

9. A linear polymer which is the product oi a transesterification reaction under heat between 2-amino-4,6-dimethcxy-1,3,5-triazine and triethylene glycol.

10. A linear polymer which is the product of a transesterification reaction under heat between 2'-amino-4,6-diethoxy-1,3,5-triazine and diethylene glycol.

11. The method of preparing new synthetic compositions which comprises effecting reaction under heat between ingredients including 1) a triazine derivative represented by the general formula where R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and R represents a monovalent hydrocarbon radical and (2) a polyhydric alcohol in which the hydroxy groups are members of the class consisting of primary and secondary hydrcxy groups, the hydroxy groups being the only reactive functional groups which are present in the said polyhydric alcohol.

12. The method of preparing linear polymeric materials which comprises eflecting a transesteriilcation reaction under heat between ingredients including (1) a triazine derivative represented by the general formula BIO- -OR' where It represents a member or the class consisting of hydrogen and monovalent hydrocarbon radicals and R represents a monovalent hydrocarbon radical and (2) a dihydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein.

13. The method of preparing linear polymeric materials which comprises heating, at a temperature not exceeding about 0., a mixture containing (l) a triazine derivative represented by the general formula where R represents a monovalent hydrocarbon radical. (2) a dihydric alcohol in which the hydroxy groups are primary and are the only reactive iunctional groups present therein, the reactants of (1) and (2) being in approximately equal molar proportions, and (3) a catalyst which is an alkali metal, and removing the volatile matter evolved during the reaction from the reaction vessel as transesterification between the reactants proceeds.

14. The method of preparing linear polymeric materials which comprises effecting a transesteriflcation reaction by heating, under reduced pressure and at a temperature not exceeding about 155 C., a mixture containing (1) a 2- amino-4,6-dialkoxy-1,3,5-triazine, (2) a dlhydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein. the reactants of (1) and (2) being in approximately equal molar proportions, and (3) a catalyst which is an alkali metal, the said catalyst being employed in an amount, calculated as alkali metal, corresponding to at least 1.5 mol per cent of the molar amount of the triazine derivative of (1) employed, and removing the byproduct alcohol from the reaction vessel as transesterification between the reactants proceeds.

15. The method of preparing linear polymeric materials which comprises effecting a transecterification reaction by heating, under reduced pressure and at a temperature not exceeding about 155" C., a mixture 01 (1) a 2-amino-4,6- dialkoxy-i,3,5-triazine, (2) a dihydric alcohol in which the hydroxy groups are primary and are the only reactive functional groups present therein, the reactants of (1) and (2) being in approximately equal molar proportions, and (3) a sodium alcoholate in an amount, calculated as sodium, corresponding to from about 2 to about 10 mol per cent of the molar amount of the triazine derivative 01' (1) employed, and distilling the lay-product alcohol under reduced pressure from the reaction vessel as transesterification between the reactants proceeds.

16. A method as in claim 13 wherein the catalyst of (3) is an alcoholate of an alkali metal.

17. A method as in claim 14 wherein the cata lyst of (3) is an alcoholate of an alkali metal.

FREDERIC C. SCHAEFER.

30 REFERENCES ormm The following references are of record in the file of this patent:

UNITED STATES PATEN'IS Number Name Date 2,197,357 Widmer Apr. 16, 1940 2,211,710 Zerweck Aug. 13, 1940 2,275,467 Pollack Mar. 10, 1942 2,296,823 Pollack Sept. 2!, 1942 2,381,121 Ericka Aug. 7, 1945 

